Organically substituted sodium aluminum hydrides and method of making and using the same

ABSTRACT

THE PRESENT INVENTION RELATES TO SODIUM ALUMINUM BYDRIDES SUBSTITUTED BY ORGANIC GROUPS.

United States Patent 3,829,449 ORGANICALLY SUBSTITUTED SODIUM ALUMI- NUMHYDRIDES AND METHOD OF MAKING AND USING THE SAME Jaroslav Vit, BohuslavCasensky, and Milan Marnula,

Prague, and Jiri Machacek, Rez. Czechoslovakia, assignors toCeskoslovenska Akademie Ved, Prague, Czechoslovakia No Drawing. Originalapplication Nov. 10, 1966, Ser. No. 594,971, now Patent No. 3,652,622.Divided and this application June 24, 1971, Ser. No. 136,594 Claimspriority, application Czechoslovakia, Nov. 13, 1965, 6,771/65; Mar. 26,1966, 2,009/66, 2,010/66 Int. Cl. C07d 5/16, 7/14 US. Cl. 260-3453 5Claims ABSTRACT OF THE DISCLOSURE The present invention relates tosodium aluminum hydrides substituted by organic groups.

This application is a division of S.N. 594,971 filed Nov. 10, 1966, nowUS. Pat. 3,652,622.

The present invention relates to a method of producing substitutedaluminum hydrides, to novel substituted aluminum hydrides and to amethod of carrying out reductions and a method of utilizing substitutedaluminum hydrides as reducing agents and as catalysts.

More particularly, the present invention is concerned with a method ofproducing sodium aluminum hydrides which are substituted with organicgroups, with novel sodium aluminum hydrides substituted with organicgroups, and with a method of carrying out reductions and catalyticallyfavored direct synthesis, utilizing the novel organically substitutedaluminum hydrides of the present invention.

Certain organically substituted sodium aluminum hydrides, for instancesodium aluminum ethoxy hydride, methoxy hydride and aryloxy hydrides areknown and used as specific reducing agents in organic chemistry. It ispossible, for instance, by using these compounds as reducing agents toreduce aldehydes, ketones and organic acid esters and chlorides toalcohols, to reduce nitro-compounds to amines and nitriles to aldehydes.Furthermore, these compounds are useful as dehalogenating agents.

Various processes have been described for producing these compounds.

One of the difliculties encountered in producing these compounds andalso in using the same is that they are only soluble in very few organicsolvents, for instance in diethyl ether but not in solvents which aremore easily available and less dangerous to handle. Thus, for instance,it is not possible to dissolve the above mentioned organicallysubstituted sodium aluminum hydrides in benzene.

This limited solubility creates'difliculties and dangers in theproduction as Well as in the use of these known products.

Some other hydrides for instance decaborane are soluble in non-polarmedia, however, in such solution these hydrides do not possess anyreducing properties.

It is therefore an object of the present invention to overcome the abovementioned difliculties and disadvantages.

It is a further object of the present invention to provide a method forproducing organically substituted sodium aluminum hydrides which can becarried out in a simple and economical manner.

'It is yet another object of the present invention to provide a methodfor producing organically substituted sodium aluminum hydrides which canbe carried out in a non-polar media.

Patented Aug. 1 3, 1 914.

It is still a further object of the present invention-to, provideorganically substituted sodium aluminum hy-g drides which are soluble incertain organic ,nonapolar me; dia such as benzene, toluene andthewlike.

In is still another object of the presentjinvention, to provide a methodof carrying out reducing reactions,-=;uti; lizing organicallysubstituted sodium aluminum hydrides as the reducing agents, whichreactions can becarried'out inanon-polar media. 1;.

It is an additional object of the present invention to provide a methodfor the direct synthesis of sodiumfalu-y minum hydrides, particularlysodium aluminum tetrahyv. dride and trisodium aluminum hexahydride. .tIFH"; 1

Other objects and advantages of thepresent invention will becomeapparent from a further reading ofltheu'iescription and of the appendedclaims. x :5

With the above and other objects in view, the present inventioncontemplates a method of producing organically substituted sodiumaluminum hydrides=ofzthe general formula (1) NaAlI-I,,Z.,

wherein x is an integral number between 1 and '2. inclusive and Z isselected from the group consisting of Q and X, wherein Y is selectedfrom the group consisting" of methoxyl, ethoxyl and propoxyl, andwherein Q is an organic rest derived by splitting off an active hydrogenatom from a compound selected from the group consisting of: (1)tetrahydrofurfuryl alcohols,

(2) tetrahydropyranyl alcohols v (3) ether alcohols of the typeobtal'able alkyla ng one hydroxyl group in diols ortwo1'hydroxylgroi1ps' "in tr-iols. (4) polyether alcohols of the-"typeobtainable by dehydration of ether alcohols and diols or by dehydrationof tetrahydrofurfuryl alcohols and diols, or by dehydration oftetrahydropyranyl alcohols and diols,

'(5) the compounds of groups (1)44), wherein at least one oxygen atom isreplaced'by a sulphunatom, (6) an amino alcohol of the general formula R'R"N(OH 3 OI-I, wherein R" and R-' are each "Se lected from the groupconsisting of alkoxyalkyl of the for mula R'O'('CH and R, and wherein Ris sel'cted from the group consisting of alkyl with 1-4 carbonatom'sandaryl with 68 carbon atoms, and wherein z isan'imegral number between 2and 4 inclusive, comprising the step of reacting at least one substanceselected from 'the group consisting of Na AlI-I and NaAlH 'with acompound' of the general formula AlZ wherein Z has the samernealiing asdefined above. "j

The term propoxyl is meant t'odenote'not only'normal propoxyl but alsoisopropoxyl. Na AlH may be prepared for instance. by the methoddescribed in Czechoslovak Pat. No- 117,768.

Compounds of the general formula A12 and also of the general formula NaZwhich may be also used as a supplementary reactant as will bedescribedin detail further below, may be prepared by the reaction of therespective alcohol with the metal, i.e., with'sodium or aluminum, orwith the respective hydride, i.e., sodium hydride or aluminum hydride.There is no difiiculty involved in preparing the thioalkoxy,dialkylamino and alkylamiuo substituted derivatives. In the case ofthe'preparatio'n of the thioalcoholates of the types NaZ and- AlZhowever, it is recommended to start from the more reactive hydrides NaHand ME, instead of the metals. The reactions, generally, may be carriedout in liquid media such as hydrocarbons, ethers (diethylether,monoglyme, tetrahydrofurane) using an excess on theZH compounds.

The thus formed NaZ compounds are insoluble in the reaction medium andthus will be formed as a suspension. Prior to being used in the abovedescribed process of the present invention which may be carried out forinstance as described in equations 7-13 and -19 below, the NaZ compoundsmust be separated from the suspension preferably by filtration andsubsequent drying. The thus obtained dry' product may be used directlyas a starting material for the method of the present invention. It doesnot require any further purification. The impurities which might bepresent such as metallic sodium do not interfere with the reaction sincethese impurities are insoluble in the reaction medium, whereas thefinished prod ucts obtained by the method of the present invention willbesoluble in the respective reaction medium. However, if the compound ofthe type NaZ has been made by using NaH as starting material andtherefore the thus produced NaZ may contain residual NaH it might bedesirable in certaincases to increase in the method according to thepresent invention the amount of the sodium aluminum hydride and A12above the theoretically required amount.

The preparation of alcoholates, aminoalcoholates, and thioalcoholates ofthe type .AlQ is equally simple. Conventional methods may be used in thepreparation of all derivatives, starting from the aluminum or aluminumhydride, and the respective alcohol, aminoalcohol or thioalcohol of theformula QH, the latter being easily removed from the product AiQg whenstripping off the solvent; subsequently, the product AlQ is dried invacuo. The above sodium aluminum hydrides, substituted according to thisinvention are all soluble in hydrocarbons and ethers; thus unalteredaluminum or aluminum hydride can be easily removed by filtration priorto the actual isolation of the final product. Thethioalkoxy-derivatives, however, having a SAl bond in their molecule,are distinguished by somewhat lower solubility.

Another very advantageous method of producing aluminum alcoholates andthioalcoholates of the type AlQ is basedon the following equilibriumreaction:

It is advisable to use an excess of QH and to carry out the reactionunder simultaneous removal of CH OH (or ROH), the boiling point of whichmust be lower than that of QH, which usually will be the case. Thestripping off of the CH OH (ROH) may be conveniently carried out byusing a rectification column.

The starting aluminum alcoholates to carry out the reaction are easilyaccessible in a pure state, even on an industrial scale. To start fromAl(OCH seems to be most advantageous since the same is insoluble, e.g.,in hydrocarbons, thus facilitating the separation. of any unalteredportion thereof from the reaction mixture. The product AlQ may beisolated by simply stripping off the solvent and the excess of QH.

The starting compound of the type NaZ.AlZ may be prepared by thereactions accounted for as below:

The complex alcoholates of the type Na'Z.AlZ are generally easilysoluble in ethers and the NaQAlQ alcoholates even in aromatichydrocarbons. Thus, they may be easily prepared according to theequations given above under the same conditions as when starting fromsimple alcoholates of the type NaZ+AlZ The method of the presentinvention may be carried out in accordance with the following equations:

In a similar manner complex compounds of the general formula NaZ.AlZ maybe used instead of A12 for instance in accordance with the equations15-,19 further below.

It is generally known that sodium alcoholates and aluminum alcoholatesreact to yield complex alcoholates according to the following equation:

wherein X is an alkyl or an aryl. The only condition for carrying outthis reaction is that of solubility. Al(OX) and the product NaAl(OX)must be soluble in the solvents used. The alcoholates of the type AlQand NaQ.AlQ are generally more easily soluble in ethers and in aromatichydrocarbons than the alcoholates of the type Na(OX).Al(OX) wherein X isthe same as mentioned above and they always result as an intermedialproduct of the reactions 7 to 13. If the complex alcoholates of the typeNaZ.AlZ are used as the starting product according to our invention therespective reactions are accounted for by the following equations:

The liquid reaction medium on which the above described reactions of thepresent invention are carried out is preferably selected from the groupconsisting of hydrocarbons and ethers which at atmospheric pressure havea boiling point lower than the docomposition temperature of thesubstituted sodium aluminum hydride which is to be produced.

One suitable manner of carrying out the reaction is under reflux atsubstantially the boiling temperature of the reaction mixture. Theliquid reaction medium preferred is benzene or toluene but, however, anyof the liquid reaction media described above may be used.

The novel hydrides of the present invention are compounds of the generalformula:

NaAlI-I stance,

NaA1Hx(O 0111i 0 4- (2) tetrahydropyranyl alcohols, so as to form, forinstance,

NeAlH; OCHI -x,

(3) ether alcohols formed for instance by alkylating one hydroxy groupin diols so as to form, for instance, NaAlH [O(CH OR'] or two hydroxylgroups in triols, so as to form, for instance,

(CH2)w-1OR' 4x, wherein R is an organic rest selected from the groupconsisting of alkyl with 1-4 carbon atoms and aryl with 6-8 carbonatoms, and z and w are each in an integral number number between 2-4inclusive, and z and w may be the same or-different.

(4) polyether alcohols obtained by dehydration of ether alcohols anddiols, so as to form wherein R has the same meaning as above and w and zare each integral numbers between 2 and 4 inclusive.

(5) polyether alcohols obtained by dehydration of tetrahydrofurfurylalcohols and diols, so as to form NBAIH O(CH1)10 CH5] 0 wherein 2 hasthe same meaning as above.

(6) polyester alcohols obtained by the dehydration of tetrahydropyranylalcohols and diols, so as to form NaAlH; 0 (CH1) 0 CH wherein 2 has thesame meaning as above.

(7) any of the compounds described in numbered paragraphs 1-6 above, inwhich one or more or all oxygen atoms are replaced by sulphur atoms, soas to form same meaning as above.

(8) an amino alcohol of the general formula R"R"'N(CH OH,

wherein R" and R' each have the same meaning as R and R" and R may be'identical or difierent, so as to form NaAlH [O(CH NR"R'] wherein 2, R"and R have the same meaning as above.

The sulphur-containing compounds including the organic rest described asQ above may be such that all oxygen atoms are replaced by sulphur or,may contain sulphur as well as oxygen atoms;

Groups of compounds which fall within the scope of the present inventioninclude:

N 8AlH O CHI-U) NaAlHn OCH NBAIHAOCHzCHzO 'h-x,

NaAlHAOCHzCHzCHzO B')4-x.

NaAlHxlO (CH1) I0 (CH2)wO R'la-x.

NaAlH; 0 (CH1) '0 CH -U NaAlH, 0 (C H1) .0 CH

and x z R, R" and R' have the same meaning as described above.

mama 00ml 0 I NaAlHi OCH 0 /CH:0C NaAlH: OCH

CHzOCHa NaAlH OCHal 0 NaAlH OCH a, naainrownanncmhh, 7 NaAlH[O(CHz):s)1]!,

Nammo(cHmNwmomooHmh,

' CHxOCHa NaAlH OCH CHzOCH: s,

It is also within the scope of the present invention to provide a methodof producing at least one sodium aluminum hydride selected from thegroup consisting of NaAlH and Na AlH comprising the step of reactingmetallic s0diun1 and metallic aluminum with hydrogen preferably at anelevated hydrogen gas pressure and at an elevated temperature in thepresence of a substituted sodium aluminum hydride as defined hereinbefore.

According to afurther variation, the present invention is also concernedwith carrying out reducing and dehalogenizing reactions by reacting areducable organic compound such as an aldehyde, ketone, ester,carboxylic acid, halide, of carboxylic acid, dialkyl amides, diarylamides andaromatic nitro compound, or with a halide which may be anorganic or inorganic monoor polyhalide also including substitutedhalides such as silicon alkyl or aryl halides for instance of thegeneral formula R SiX wherein R is alkyl or aryl and X is a halogen.

The substituted sodium aluminum hydrides of the pres ent invention maythus be used as reducing agents soluble in non-polar media and ascatalysts for the direct synthesis of complex sodium aluminum hydridesfrom free elements, i.e., from sodium, aluminum and hydrogen.

These substituted complex sodium aluminum hydrides will reduce innon-polar media, e.g., in benzene, the derivatives of organic acids,ketones and aldehydes to alcohols in the same way and to the same extentas it would be possible with non-substituted complex aluminum hydridesin ethers. In contradistinction to the properties of the known complexaluminum hydrides, they will even dehalogenate the alkyl and arylhalides, and they will reduce the nitro derivatives to azo-compounds.All the aforementioned reactions will proceed in ethers as well as innon-polar media.

The following Examples are given as illustrative without, however,limiting the invention to the specific details of the Examples.

EXAMPLE I An apparatus as described in Example II was charged with 2.1g. of an 80% solution of Na AlH (0.0164 mol) and 50 ml. of benzene. Themixture was refluxed under dropwise addition of 8.27 g. of Al(OCH CH OCH[0.0328 mol] dissolved in ml. of benzene. The reaction mixture was keptboiling under stirring for an additional 30 minutes. Upon subsequentfiltration, and evaporation of the solvent, 9.36 of NaAlI-I (OCH CH OCHwas obtained, i.e., 94.1% of the theory.

The starting compound Al[OCH CH OCI-I was prepared by the followingreaction:

AI[OCH CH OCH +3CH OH. The above reaction was carried out with a 160%excess on CH OCH CH OH.

(Instead of using an excess of CH OCH CH OH, the theoretically requiredamount may be used and the excess of this compound replaced with anothersolvent, preferably benzene or toluene.) The methyl alcohol evolved wasdistilled off from the reaction mixture during the re action, using arectification column. Subsequently to stripping off the methyl alcohol,the excess of cmocn cn on was stripped oif under vacuum. The product ofthe reaction is a liquid highly viscous compound of the formula Al(OCHCH OCH intermiscible with benzene, toluene, and others in any ratio.

EXAMPLE II Into a three-necked round-bottomed flask of 100 ml. volume,provided with a stirrer, a reflux water-condenser and dropping funnel,1.7 g. of Na AlH of 85% purity was charged (the remaining consisting ofaluminum and silicon), and 35 ml. of tetrahydrofurane was added. Themixture was heated to boiling and a solution of 8.26 g. Al[O.CH CH N(CHin 15 ml. tetrahydrofurane was added dropwise under stirring. Theheating was discontinued after 45 minutes and the mixture was cooled to15 C. Subsequent to filtration, the tetrahydrofurane was stripped offfrom the filtrate, and the thus obtained residue was dried at 100 C. ata pressure of 0.1 mm. Hg; 9.1 g. of a compound of the formula NaAlH [QCHCH N (CH 2]:

was obtained, i.e., 93.5% of the theory according to equation 8. The (CHNCH CH OH required for preparation of Al[OCI-I CH N(CH was prepared by areaction which is well known in the methylation of primary amines toconvert the latter into tertiary amines, starting with HzNCHzCHgOH,formaldehyde and formic acid. The starting Al[OCH CH N (CH was preparedfrom aluminum methylate in a manner similar to that described in ExampleI, with respect to the preparation of Al(OCH CH OCH EXAMPLE III Into a2.5 1. pressure vessel, 46 g. of sodium (2 moles), 32.9 g. of aluminumpowder of 82% purity (the balance up to 100% consisting of aluminumoxide), 50.5 g. of NaA1I-I (OCH CH OCH [0.25 moles), and 500 ml. ofbenzene was added and a stirring bar inserted into the pressure vesselfor stirring of the reaction mixture. Hydrogen was fed into the vesselto establish a pressure of atoms. The reaction was then carried out at atemperature of C. for a period of 3 hours. The reaction mixture wasfiltered and the solid residue extracted with benzene; 55.4 g. of solidNa AlH was obtained of 88.5% purity, i.e., 96.1% of the theory. Thebenzene filtrate contained dissolved sodium aluminum alkoxyhydrideswhich were being used as catalyst in the following synthesis.

EXAMPLE IV The direct synthesis of both sodium aluminum hydrides NaAlHand Na AlH proceeds similarly even if other compounds of the type NaAlfiQ e.g.,

NaAlH [0 (CH OC 3] a,

or NaAlH [0(CH N(CH are used as a catalyst; the sulphur compounds,however, being less suitable than the other compounds of the formulaNaAlH Q The pressure of hydrogen applied may be in a very broad rangefrom 2 to 200 atmospheres. At pressures lower than 2 atmospheres,however, the reaction is too slow; increasing the pressure above 200atmospheres does not influence the reaction rate substantially, thus afurther increasing of the pressure above 200 atmospheres is notpractical. The quantity of the catalyst applied can very in the rangefrom 0.5 to 100% in respect to the amount of sodium and aluminum used.In the specific Example III and Example IV, about 50% of the catalystwas used.

Smaller amounts of the catalyst, below 0.5% result in decreasing of thereaction rate. i

Using a greater amount of catalysts is of no inconvenience as thecatalyst may easily be recycled.

It is advisable to mill the reaction mixture thoroughly prior to theactual synthesis.

EXAMPLE V Into a 1 liter three-necked vessel, provided with a stirrer, awater cooler, and dropping funnel were charged; 2.75 g. NaAlH [98.2%],200 ml. benzene, and 8 g.

MpW

The reaction mixture was refluxed under dropwise addition of a solutionof 21.9 g.

tion residue was dried at 100 C. and 0.1 mm. Hg. The

yield was 32 g. of

which corresponds to 98.16% of the theory. The starting compound of theformula Q0 CHaCHzOH was prepared in toluene by the well known reactionaccounted for by the following equations NaH @on--Nao- 11,,

oiomomon Na0 noomomo-G N801 9 The starting Was prepared from aluminummethylate by reactions similar to those described in Example I. Thealcoholate Naoonicnio was prepared in a refluxing mixture of toluene,sodium hydride and Q crttcmon in a excess. The toluene and the excessiveClIICl alcohol were stripped off in vacuo and the remaining portions ofthe said compounds were distilled off at 0.05 mm. Hg and 160 C.

EXAMPLE VI The same apparatus as in Example V was charged with 5.6 g. NaAlH [91.1%], 500 ml. benzene, and 26.1 g.

The reaction mixture was refluxed under dropwise addition of a solutionof 120 g.

in 200 ml. benzene across a period of minutes. The reaction mixture upontreatment as described in Example V yielded 147.2 g.

i.e., 97.36% of the theory.

To prepare NaO omomoomand use was made of the same methods as describedin Example V.

EXAMPLE VII The same apparatus as in Example V was charged with 2.75 g.NaAlH [98.2%], 2.5 g. NaH [96.0%] and 150 ml. toluene. The reactionmixture was refluxed under dropwise addition of a solution of 29.4 g.

A1(OCH CH CH OCH in ml. toluene across a period of 45 minutes. Upontreatment of the reaction mixture in the manner described in Example V,34.0 g. of

NaAlH (OCH CH CH OCH 2 was obtained, corresponding to 98.57% oftheoretical yield.

The necessary CH OCH CH CH OH required for preparation of AI(OCH CH CHOCH was prepared by the methylation of one hydroxy group in1,3-propanediol, using sodium hydride and (CH O) SO The latter reactionwas carried out in boiling toluene. The starting Al[OCH CH CI-I OCH wasprepared from aluminum methylate in the same manner as described inExample I.

EXAMPLE VIII Into the same apparatus as described in Example V, werecharged: 2.75 g. of NaAlH [98.2%], 26.1 g. of

1%(0 omorncmo 10 and 500 ml. of benzene. The reaction mixture wasrefluxed under simultaneous dropwise addition .of asolution of 72 g.

Ai(oornomcrno) in ml. benzene, across a period of 45 minutes. Treatmentof the reaction similar to that described in Example V gave 99.51 g.

i.e., 98.72% of the theory.

In the preparation of the start ing compound use was made of the samemethod as described in Example V.

EXAMPLE IX The same apparatus as in Example V was charged with 5.6 g. NaAlH [91.1%] and 250 ml. benzene. The reaction mixture was refluxed underdropwise addition of a solution of 38.4 g. Al(OCH CI-I OCH CH OCH in 8.0ml. benzene. Further treating ofthe reaction mixture-as described inExample V yielded 42 g.

in 150 ml. benzene.'The same treatment of the reaction mixture as inExample V gave 43.2 g.

which is 97.74% of the theory.

The I v I @o omomcmo ontomorr required for preparation of NaAlOCHzCHzOCH CHzCHzOQ) was prepared in the following manner: The sodiumphenolate was alkylated in boiling toluene with nocn cn c-n ci;

@o cnzonionion resulting from the reaction was isolated and converted byreaction with sodium hydride in boiling toluene into its alcoholate andthe latter was alkylated with HOCH CH Cl,

giving a compound of the formula Q-oornomomoomomon.

The starting complex alcoholate was prepared in the apparatus describedin Example V in accordance with the following equation:

NaAlH4+4 -o cmcmomo crricnzo 1r NaAl[O cmc m0 cmomcmo-] an.

NaAlHz O CHzCHzO CHzCHzCHzO 11 The alcohol was added dropwise to a 5%solution of sodium aluminum tetrahydride in tetrahydrofurane in thestoichiometrically required amount.

EXAMPLE XI The same apparatus as described in Example V was charged with5.6 g. Na AlH (91.1% 27.6 g.

and 600 ml. benzene. The reaction mixture was refluxed under dropwiseaddition of a solution of 127.6 g.

in 250 ml. across 45 minutes. Upon treatment of the reaction mixture asdescribed in Example V, 154.0 g. of NaAlH[O (CH O (CH OCH CH wasobtained, which corresponds to 96.13% of the theoretical yield.

' The alcohol of the formula C H O(CH O(CH OH required for preparationof the starting alcoholate was prepared from 1,4-butanediol byconverting one of the hydroxyl groups into alcoholate by reaction withsodium hydride in boiling toluene'and subsequent alkylation with C H Br.The product obtained, i.e., C H O(CI-I OH was reconverted into thealcoholate form by reaction with sodium hydride in boiling toluene withC H O(CH Na subsequently alkylated with ClC CH OH, giving C H O(CH O (CH0H. The starting alcoholate of the formula was prepared from aluminummethylate and c n o (CH o (CH 0H in the same manner as described inExample I. The compound of the formula NaO(CH O(CH 0C H was prepared bythe reaction of sodium hydride with C H O(CH O(CH 0H in the same manneras described in Example V.

EXAMPLE XII The same apparatus as described in Example V was chargedwith 2.75 g. of NaAlI-L (98.2%), 2.5 g. NaH (96.0%), and 300 ml.toluene. The reaction mixture was refluxed under dropwise addition of asolution of 46.25 g.

Al[0 (CHz)zO CHrl 0 I in 100 ml. toluene. Upon treatment of the reactionmixture as described in Example V, 50 g. of

was obtained, i.e., 97.4% of the theory.

The

i o LCHaO (CHzhOH required for preparation of LCHzBr and NaOCH CI-I OHin boiling toluene by the method described in Example V. The starting Al0(CH2) OCH2 O was prepared by the method described in Example I.

EXAMPLE XIII was prepared from The same apparatus as described inExample V was charged with 5.6 g. Na AlH (91.1%) and 250 ml.tetrahydrofurane. The reaction mixture was refluxed under dropwiseaddition of a solution of 22.3 g.

in ml. tetrahydrofurane for a period of 45 minutes. Upon treatment ofthe reaction mixture as described in Example V, 26.71 g. NaAlH [OC HN(C- H was obtained, i.e., 97.3% of the theory.

The starting alcoholate Al[OCH CH- N(C H was prepared from aluminummethylate and (C H NCH CH OH by the method of Example I.

EXAMPLE XIV The same apparatus as described in Example V was chargedwith 5.6 g. N33'A1H5 (91.1%), 19.2 g. Na[O(CH SC H and 450 ml. toluene.The reaction mixture was refluxed under dropwise addition of a solutionof 85.5 g. Al[O(CH SC H in 150 ml. toluene for a period of 40 minutes.Upon treatment of the reaction mixture as described in Example V, 106 g.

NaAlH [O CH SC H 3 EXAMPLE XV The same apparatus as described in ExampleV was charged with 5.6 g. Na AlH (91.1%) and 350 ml. benzene. Thereaction mixture was refluxed under dropwise addition of a solution of59.5 g.

in ml. benzene for a period of 45 minutes. Upon treatment of thereaction mixture a described in Example NaAlHz[0(CHz) morn-U11,

which corresponds to 96.14% of the theory were obtained.

In preparation of the starting material first the compound of theformula i i-CHgS(CH2)iOII i LCHzSH by conversion of the latter intoLCHZSNB using sodium hydride in boiling toluene. The subsequentoperation was alkylation of the mercaptide formed, i.e.,

of the mercaptide i LCHzSNa with HO(CH Br. The thereby obtained producti o LCHZS (CH2)4OH was converted into sodium alcoholate i oLCHzS(CH1)4ONa by the method of Example I.

EXAMPLE XVI The same apparatus as described in Example V was chargedwith 5.6 g. Na AlH (91.1%) and 250 ml. toluene. Under refluxing thereaction mixture, 34.2 g. Al[SC H OC H dissolved in 100 ml.tetrahydrofurane was added dropwise over a period of 45 minutes. Upontreatment of the reaction mixture as described in Example V, 38.6 g.NaAlH [SC H OC H was obtained, i.e., 98.22% of the theory.

The required mercaptane C H OC H SI-I was prepared by conventionalsynthetic methods from via a thiouronian salt. The aluminum mercaptidewas prepared from the mercaptane obtained, by the reaction with aluminumhydride in tetrahydrofurane in a solution containing stoichiometricratios of the reactants.

The solution obtained was subsequently analyzed and, upon adjustment ofconcentration, used directly in the above preparation of NaA1H [SC H OCI-I EXAMPLE XVII HSCH CH SH The HSCH CH SH was converted to HSCH CH SNaby the reaction with sodium hydride in boiling toluene and themercaptide was subsequently treated under reflux was prepared from 14with (CH OMSO added in a molar ratio of 1:1. The aluminum mercaptide wasprepared in the same way as described in Example XVJI.

EXAMPLE XVIII The same apparatus as described in Example V was chargedwith 5.6 Na AlH (91.1%) and 150 ml. tetrahydrofurane. Under refluxing ofthe reaction mixture, 50.7 g. Al[SC H NCH(C H,-,) dissolved in 250 ml.tetrahydrofurane was added dropwise over a period of 45 minutes. Upontreatment of the reaction mixture as described in Example V, 53.79 g. of

was obtained, i.e., 96.41% of the theory.

The amino mercaptane required was prepared from (C H NCH CH Cl via thethiouronian salt. The

(C H NCH CH SH thus obtained was used in the preparation of Al[SCH CI-IN(C H from aluminum hydride and tetrahydrofurane in the same manner asdescribed in Example XVI.

EXAMPLE XIX The same apparatus as described in Example V was chargedwith 5.6 g. Na AlH (91.1% and ml. tetrahydrofurane. The reaction mixturewas refluxed under dropwise addition of a solution of 144.4 g.

NaAl (SC4H3SCZH5) 4 in 500 ml. tetrahydrofurane. Upon treatment of thereaction mixture as described in Example V, g.

was obtained, i.e., 97.06% of the theory.

The necessary mercaptane was prepared from by substitution of thebromine atoms with SH groups via thiouronian salt. The SH(CH SI-I- thusobtained was converted into its sodium salt by reaction with sodiumhydride in boiling toluene; the salt was alkylated with ethyl bromidealso in toluene. The C H S(CH SH thus obtained was used in thepreparation of the complex mercaptide starting from sodium aluminumtetrahydride. The reaction was carried out in tetrahydrofuran underreflux with theoretical amounts of the reactants according to thefollowing equation:

The thus prepared solution was used directly (subsequent to analysis andadjustment of the concentration) in the preparation of the respectiveorganically substituted sodium aluminum hydride of this Example.

EXAMPLE XX The same apparatus as described in Example V was charged with5.6 g. Na AlH (91.1%) and 100 ml. tetrahydrofurane. The reaction mixturewas refluxed under dropwise addition of a solution of 33.9 g.

in 200 ml. tetrahydrofurane for a period of 45 minutes. Upon treatmentof the reaction mixture as described in Example V, 37.8 g. NaAlH [SC HN(CH was obtained, i.e., 96.9% of the theoretical yield. The requiredaminomercaptane was prepared from (CH NCH CH CL via the thiouroniansalt. By the procedure described in the Example XVIII, the compound (CHNC H SH was converted into the aluminum mercaptide 1 EXAMPLE XXI Thesame apparatus as described in Example V was charged with 63 g.-NaAlH[OC H N(CH and 250 ml. benzene. The reaction mixture was refluxedunder dropwise addition of 14 g. benzoyl chloride for 30 minutes;subsequently, 50 ml. benzene was added and the reaction mixture wasrefluxed for additional 2 hours and, subsequent to cooling, hydrolysis,and addition of HCl, 9.75 g'. of benzyl alcohol was isolated, i.e.,90.16% of the theory.

EXAMPLE XXII The same apparatus as described in Example V was chargedwith 55.2 g. NaAlH[OCI-I CH OCH and 200 ml. benzene. The reactionmixture was refluxed under addition of g. ethyl benzoate with 50 ml.benzene for a period of minutes. After an additional 2 hours ofrefluxing, the mixture was cooled, and hydrolysis and isolation yielded8.76 g. benzyl alcohol, i.e., 81% of the theory.

EXAMPLE XXI-II In a similar manner to Example XXII, the followingcompounds were reduced under substantially the same reaction conditions,and with the same solvents molar concentrations and molar ratios of thereactants:

Reaction time Yield Starting Compound Product (hours) (percent)(CHsCO)zO CzH5OH 2 91.2 n-C3H1COOC1H5 C4HQOH 2 89.0 C2H5COON(CH3)2CaH7OH 4 62.8

The procedure, however, is not limited to the use of the compounds givenabove. Under the same conditions any other compound of the type NaAlI-I,Q may be used as for example NaAlH (OCH CH OCH W mp or NaAlH [OCI-I OCHOCH To reduce 1 g. mol of a compound containing one single carbonylgroup (-CH-O or -CO-) into the respective alcohol the theoreticallynecessary amount of NaAII-I Q is equal to l/x grammole of NaAlH toreduce one gram mole of a compound containing one single carboxyl groupin the molecule the amount necessary of the compound NaAlI-I, Q is equalto 2/x gram mole of NaAlH Q EXAMPLE XXIV In an apparatus as described insion of 5.6 g. trisodium aluminum hexahydride of 91.1% purity in 250 ml.of benzene was prepared. The suspension was heated to boiling and'asolution of 37.2 g.

Example V, a suspenin 80 ml. benzene was added dropwise over a period of30 minutes. By the method of Example V, 39.8 g. of

main. OCH I was obtained, which corresponds-to 94% of the theory.

The starting was prepared by reacting aluminum methylate with a solutionof O-CH2OH in toluene as a solvent, in which solution toluene and LCHzOH were present in a ratio of 1:1, the said L CHQOH was used in anexcess which corresponds to 150% of the theoretical amount needed. Inaccordance with equation 1, methylalcohol was stripped off from thereaction mixture in a rectification column; subsequently, toluene wasstripped ofi at atmospheric pressure and, finally, the excess of \OCHzOH was stripped off in a partial vacuum at a temperature of up to 150C. The product was a non-distillable, highly viscous matter,intermiscible with benzene, toluene, and ethers in any ratio.

EXAMPLE XXV In the same apparatus as in Example V, a suspension of 5.6g. trisodium aluminum hexahydride of 91.1% purity in 250 ml. benzene wasprepared. The suspension was refluxed and a solution of 33.3 g.

Al[OCH CH CH N (CH 2 in ml. benzene added during a period of 30 In thesame manner as described in Example V, of NaAlH [OCH CH N(CI-I wasobtained.

To prepare the starting reactant first (CH NCH CH CH OH had to beprepared from HOCH CH CH NH by the contional reaction with formaldehydeand formic acid;

was then prepared from (CH NCH CH CH OH in the same manner as describedin Example XXIV. The former compound is a highly viscous non-distillableliquid, intermiscible with benzene, toluene and ethers in any ratio.

EXAMPLE XXVI minutes. 36.7 g.

To a refluxing suspension of sodium hydride in xylene (200 ml. of xyleneper 1 gram mol sodium hydride), Na(CH CH OH) was added dropwise understirring, and heating was prolonged until evolution of hydrogen hadsubstantially stopped. Subsequently, (CH O) SO was added under the sameconditions, and the refluxing was resumed and continued under theevolution of hydrogen terminated. The mixture was allowed to cool and100 ml. of a 60% water solution of potassium hydroxide added per onegram mol of (CH O) SO used. Then, the reaction mixture was filtered, thesolid phase washed with xylene and from the xylene solutions HOCH CH NCH CH OCH 2 was extracted with water, neutralized and slightly acidifiedwith hydrochloric acid. The hydrochloride obtained was isolated byevaporation of water in vacuo, and the base was set free by addition ofa 70% water solution of potassium hydroxide which was added in a slightexcess not higher than 10% over the theoretically required amount. Themixture was stirred with diethyl ether and the precipitated potassiumchloride was filtered ofl. The product (CH OCH CH NCH CH OH was obtainedfrom the ethereal solution by distillation and converted into itsaluminate in the same manner as described in Examples L and XXIV.

EXAMPLE XXVII In the apparatus described in Example V, a suspension of5.6 g. of Na AlI-I of 91.1% purity was prepared in 250 ml. benzene. Thesuspension was refluxed, and a solution Of g. in 120 ml. benzene addeddropwise over a period of 30 minutes. In the same way as described inExample V, 72.1 g. Of was obtained which corresponds to 93.2% of thetheory.

The starting amino alcohol was prepared from HOCH CH NH by alkylation ofCH OCH CH CH CH CL The latter compound was prepared by methylation ofone hydroxyl group in 1,4-butane diol and by subsequent conversion ofthe second hydroxyl group into chloride by reaction with thionylchloride. The necessary (CH OCH CH CH CH NCH CH O] A1 was prepared inthe manner described in Examples I and XXIV.

EXAMPLE XXVIII In the apparatus described in Example V, a suspension of5 .6 g. of trisodium aluminum hexahydride (0.05 mol) of 91.1% purity wasprepared in 250 ml. benzene. The

18 suspension was refluxed and a solution of 38.4 g. of Al[OCH(CH 0CH inml. benzene was added over a period of 30 minutes. In the same manner asdescribed in Example V, 55.6 g. of

NaAlH [OCH(CH OCH 2 was obtained, which corresponds to of the theory.

The starting (CH OCH CHOH was prepared from glycerol by methylation oftwo hydroxyl groups by reaction with sodium hydride and (CH O) SO in asimilar manner as described in Example XXVI. The ether alcohol obtainedwas used in the reaction with aluminum methoxide to prepare the startingAl[OCH(CH OCH in the manner described in Example V.

EXAMPLE XXIX In the apparatus described in Example V, a suspension wasprepared of 5.6 trisodium aluminum hexahydride of a 91.1% purity in 200ml. tetrahydrofurane. Under the conditions described in Example V, asolution of 20.4 g. of (n-C H O A1 in 200 ml. tetrahydrofurane wereadded. Identical procedure as described in Example V afforded 24.1 g. ofNaAlH [O(n-C H 1 i.e., 94.3 %of the theory.

EXAMPLES XXX TO XL In the apparatus described in Example V, and underthe same conditions as described therein, further compounds of theformula NaAlHQ were synthesized according to the equation wherein thediflerent radicals Q are defined in the Table 1 below.

In the apparatus described in Example V, a suspension was prepared of2.75 g. of sodium aluminum tetrahydride (0.05 mol) of a 98.2% purity andof 0.15 mol alcoholate of the type NaQ wherein Q again has the severalmeanings listed in the Table below. The reaction medium was 200 ml.benzene. The reaction mixture was refluxed at ambient pressure and asolution of 1.15 mol of AlQ in ml. benzene was added dropwise across aperiod of 30 minutes. The reaction mixture was refluxed for anadditional 4 hours. Upon cooling to 15 C., the clear solution wasfiltered off and the solid residue containing mostly starting materialsand impurities was washed with benzene stripped off from the filtrate.From the clear solution obtained benzene was distilled off and thecollected product was dried in vacuo at 100 C. and 0.1 mm. Hg.

The yields in gram and percent obtained with respect to the differentspecific reactants of Examples XXX to XL are also indicated in Table 1.

TABLE 1 Starting compounds Product N 210, AIQ; N aAlHQ Yield, g Q in g.in g. In g. percent CHsO (CH2)2O 14. 7 37. 8 52. 1 9. 65 C2H5O (CHz)30-16. 8 44. 1 59. 8 94. 1 CHaO (CH2)a0- 16. 8 44. 1 60. 4 95. 0 CzHsO(CH2)aO- 18.9 50. 4 68. 5 95. 1

L lCHz0 XXXV-...- 2. 75 20. 7 55. 8 74. 4 94. 4

2.75 (CHa)5N(CH2)2O- 16. 7 43. 7 60. 5 96. 1 2. 75 (C2Ha)5N(CH2)20- 20.9 56. 3 64. 9 95. 7 2. 75 (CH30 CH2CH2)2N(CH;)2O 22. 4 60. 8 61. 2 94. 62. 75 (CH3OCH2)2CHO 21. 3 57. 6 78. 3 96. 1 2. 75 CH O (CHmO (CH2)2O 21.3 57. 6 76. 1 93. 2

1 9 EXAMPLES XLI TO XLIII In the apparatus described in Example V, andunder the same conditions as described in Example XXX to XL, furthercompounds of the formula NaAlH Q were synthesized according to theequation:

TABLE 2 Starting compounds N a AlHa in g. Q,

Product AlQs N aAlHzQz 1n g. in g.

EXAMPLE XLIV Yield, percent;

Example XLI XLII..

Into a pressure vessel of 2.5 1. volume were charged 23 g. of sodium (1mol), 33 g. of aluminum powder (of 95% purity, containing aluminumoxide), 400 ml. toluene and 9.2 g. of NaAlH [O(CH N(CH equal to 16% byweight of the latter with respect to the amount of sodium and aluminumused. Hydrogen was introduced into the pressure vessel to establish apressure of 150 atmospheres. The pressure vessel was heated to atemperature 011160 to 170 C. and the pressure therein was kept at thelevel of 150 atmospheres. The reaction was finished after 4 hours andthe pressure vessel cooled and emptied. The solid phase was extractedwith tetrahydrofurane which was used in an quantity of 200 millilitersper each grams of NaAlH obtained. From the tetrahydrofurane extract 50.1g. of NaAlH was obtained subsequent to evaporation, i.e., 92.6% of thetheory.

As to the'catalyst used and as to the amount of the latter appliedconditions were maintained as described in Example III. The optimumtemperature range lies between 150 and 170 C. At temperatures below 150C. the reaction is too slow or it does not proceed at all. Attemperatures above 170 C. trisodium aluminum hexahydride is obtained asa by-product. It is also possible to work with stoichiometric amounts ofsodium and aluminum; an excess on aluminum, however, is moreadvantageous (from 10 to 50%) so as to avoid excessive formation oftrisodium aluminum hexahydride.

EXAMPLE XLV In the apparatus described in Example V, a solution of 13.4g. of p-CH C I-li NO in 100 ml. benzene was added dropwise across aperiod of 30 minutes to a refluxing solution of 40.4 g. of NaA1H [O(CHOCH (0.2 moles) in 200 ml. benzene. The mixture was refluxed for oneadditional hour and, subsequently to cooling to 20 C., 200 ml. water wasadded and the mixture was neutralizedwith theoretical amounts ofsulfuric or hydrochloric acid. The solution was filtered, thebenzenelayer removed and 9.4 g. of the compound was obtainedsubsequently to evaporation of benzene. The yield was 92% of the theory.

20 With the same result, any of the other compounds of the formulaeNaAlH Q e.g.,

NaAlHz[OCH2-[ O EXAMPLE XLVI Into a pressure vessel of 1.5 1. volume asolution oi 67 g. of NaAlH [O(CH OCH (0.33 mol) in 500 ml. of benzenewas charged and a sealed glass ampulla containing 27.11 g. of SiHCl (0.2moles) and 5 steel balls of a diameter of 30 mm. were inserted into thevessel. The pressure vessel was closed, flushed three times withnitrogen introduced at a pressure of 20 atmospheres, and the nitrogendischarged. By a sudden rotation of the pressure vessel the ampulla wasbroken. A spontaneous reaction took place and the pressure rose to 5atmospheres. The contents of the pressure vessel were emptied into a gasholder and by analysis it was determined that 4.8 1. (20 C.) of siliconhydride SiH was obtained, i.e., 96% of the theory. The other compoundsof the general formula NaAlH Q which are mentioned in Example XLX mayalso be used and will give similar results.

may be used.

EXAMPLE XLVII Under conditions identical to those of Example XLVI, thereaction of 21 g. S11 (0.2 moles) with g. NaAlH] [O(CH OCI-I (0.4mmoles) in 500 ml. benzene was carried out, giving 4.85 l. ofsilicon'hydride, SiH i.e., a yield of 97%. Other compounds of the formula NaAlI-I Q may be used in a similar manner and with the same result.

EXAMPLE XLIX Under conditions identical to those of Example XLVI, thereaction of 30 g. CH SiCl (0.2 moles) withv N aAlHzliO CHI-i O 2 (0.33moles) in 500 ml. benzene was carried out. The reaction afforded 4.44 l.of CH SiH i.e., 89% of the theory. Other compounds of the formula 1laAlH Q may be used in a similar manner and with the same result.

EXAMPLE L In the apparatus described in Example V, containing a solutionof 33.3 g. of NaAlH [OOH CH OCH (0.165 moles) in 200 ml. benzene thereaction with 21.1 g. of C H SiCl (0.1 moles) in ml. benzene was carriedout. The two solutions were added together over a period of 30 minutes,and thereafter the reaction mixture was refluxed for 30 minutes. In aconventional manner the compound of the formula C H SiH was isolated and9.3 g. of the said product obtained, i.e., 86% of the theory. Othercompounds of the formula NaAlH 44 may be used in a similar manner andwith the same result.

EXAMPLES LI TO LIH Into a rotary pressure vessel of 1.5 1. workingvolume, a solution was introduced consisting of 50 ml. benzene havingdissolved therein NaAlH [OCH CH N(CH in the amounts indicated in Table 3below. steel balls of a diameter of 30 mm. and a scaled glass ampullacon taining the halide the formula of which and the amount of which aregiven in Table 3 were also inserted into the pressure vessel. Thepressure vessel was flushed with hydrogen and the ampulla was caused tobreak in the manner described in Example LV. The pressure vessel wasrotated under heating to a temperature of 100 C. at which temperaturethe rotating vessel was kept for 2 hours. Upon cooling to 20 C., the gasevolved was discharged into a gas receptacle, the volume of the gasdetermined and the latter identified by means of gas chromatography.

22 EXAMPLE LVII A pressure vessel of 2.5 1. working volume was chargedwith 69 g. metal sodium (3 mol), 28.4 g. of aluminum powder of 90.1%purity (1 mol), 114 g. of Na AlH of 89.8% purity (1 mol), one liter of axylene solution of 95 NaAlH [OCH CI-I N(CH and 1.5 Of steel balls of 5mm. diameter. The pressure vessel was closed, flushed thoroughly withhydrogen, evacuated and heated to a temperature of 185 to 190 C. At thistemperature, hydrogen was introduced into the vessel, and the partialpressure of hydrogen was kept in a range of between 0.45 to 0.55atmospheres. When the reaction was finished and TABLE 3 Startingcompounds Product N aAlH2=[O CHaCHzN (CHO 111 Allryl halide HydrocarbonIn Liter! Example In g. In gram mols In g. g., mole 20 0. Percent LI 1410. 5 CHgCl 50. 5 1 CH; 23. 5 94 LII 282 1 C2H4Bl": 188 1 CzHl 23. 1 92LIII 141 0. 5 02114.1 156 1 CzHc 23. 8 95 EXAMPLES LXIII TO LXV Into theapparatus as described in Example V, a solution of NaAlHz O CI-Iz 1 in300 ml. p-xylene was charged (the amount used of the former compound inthe individual Examples LIV to LVI is given in Table 4). Subsequently,the mixture was refiuxed under atmospheric pressure. To the refluxingsolution was added dropwise across a period of 30 minutes a solution ofan aryl halide in 100 milliliters of p-xylene. The aryl halides used andthe amounts thereof are also specified in Table 4 below. The reactionmixture was refluxed for an additional 2 hours. Upon cooling to 20 C.,10 ml. water was added, and subsequently, 100 ml. of hydrochlorine acid.The organic layer was quantitatively separated and neutralized byshaking with 5 ml. of a 40% aqueous solution of potassium hydroxide,introduced into a 1 liter measuring flask, and xylene was added up tothe required level.

The product was identified, the yield ascertained by means of gaschromatography.

TABLE 4 Starting compounds the consumption of hydrogen stopped, thepressure vessel was cooled, emptied, the balls removed and thesuspension obtained was treated in the manner described in Example III.The synthesis afforded 205 g. of a slightly grayish matter containing191 g. of trisodium aluminum hexahydride which corresponds to a yield of94%.

The addition of trisodium aluminum hexahydride to the reaction mixtureprior to the actual synthesis is only of importance for the milling ofaluminum which otherwise would not proceed. Another material may also beused for this purpose, any inert material, as for instance alumi numoxide will give the desired result. The final product, however, is thencontaminated with the inert material added.

As to the choice of the catalyst, the same will apply as stated inExample III.

Without further analysis, the foregoing will so fully reveal the gist ofthe present invention that others can by applying current knowledgereadily adapt it for various applications without omitting featuresthat, from the standpoint of prior art, fairly constitute essentialcharacteristics of the generic or specific aspects of this inventionand, therefore, such adaptations should and are intended to becomprehended within the meaning and range of equivalence of thefollowing claims.

Product NHAITI: OCH:

O z Hydrocarbon Aryl halide Yield,

Example In g. Ingram mol In g. In gmol In g. percent LIV 30.5 0.12 w50.6 0.2 Naitalene 24.8 96.8

LV 30.5 0.12 1|3r 23.6 0.1 Benzene 7.3 93.5

I 45.7 0.18 Br 31.5 0.1 Benzene... 7.2 92.2

Br- Br 23 What is claimed as new and desired to be secured by LettersPatent is:

1. A substituted sodium aluminum hydride of the formula NaAlH Q whereinx is 1 or 2 and wherein Q is an organic residue derived by splitting ofian active 5 hydrogen atom from a compound selected from the groupconsisting of tetrahydrofurfuryl alcohol, tetrahydropyranyl alcohol,alcohols of the formula l l H0 c111 OCH and alcohols of the formula inwhich 2 is an integer from 2 to 4.

2. The substituted sodium aluminum hydride of claim 1 which is selectedfrom the group consisting of x being 1 or 2.

4. The substituted sodium aluminum hydride of claim 1 which is selectedfrom the group consisting of 5. The substituted sodium aluminum hydrideof claim 1 which has the formula References Cited UNITED STATES PATENTS3,394,158 7/1968 Chini et al. 260-448 3,629,288 12/1971 Vit 260345.1

HENRY R. JILES', Primary Examiner B. DENTZ, Assistant Examiner US. Cl.X.R. 260-397.8

